Process of treating textile materials



Patented Oct. 2, 1945 UNITED STATES PATENT OFFICE f PROCESS OF TREATING TEXTILE MATERIALS Maurice Arthur Thorold Rogers, Blackley, Manchester, England, assignor to Imperial Chemical Industries Limited, a corporation of Great I Britain No Drawing. Original application July 27, 1939,

Serial No. 286,944. Divided and this application September 5, 1940, SerialN'o. 355,453. In

. Great Britain July 29, 1938 Claims. (Cl. 8116.3)

This application is a division of my copending application Serial No. 286,944, filed July 27, 1939, and relates to the treatment of textile materials with the novel organic ammonium compounds described in said parent application. especially for the purpose of conferring water-repellent properties on said textile materials.

' According to the invention described in said parent application, new organic ammonium compounds are made by effecting combination between halogeno-methyl compounds of the general formula (where R is an aliphatic hydrocarbon radical containing not less than '7 carbon atoms, and X is a halogen) and aliphatic or heterocyclic tertiary amines.

Numerous illustratlons of applicable initial materials and details of their mode of synthesis into the desired novel ammonium compoundsare given in the parent application.

The new compounds are believed to be quaternary ammonium compounds. They are solids which are soluble in benzene, alcohol and chloroform and sparingly soluble in ether and ace-' tone. They dissolve readily in water, forming solutions which foam on shaking. When these solutions are boiled the compounds are slowly decomposed, the solutions gradually losing their foaming power. When the compounds themselves are heated to temperatures above 100 C.

they decompose rapidly, forming water-insoluble waxy substances.

Now according to thepresent invention, the said new quaternary salts are applied to textile materials which are of animal or vegetable origin or which arecomposed of regenerated cellulose or of cellulose esters or ethers to give them propertieS of softness or of softness and water-repellence, which are resistant to laundering or drycleaning treatments. This feature of the invention comprises impregnating the said textile materials with a solution or suspension of one or more of said quaternary salts in water or a suitable organic liquid, and subsequently submitting the impregnated material to a short heat treatment at a temperature such that the quaternary salt undergoes decomposition.

The conditions for carrying out the impregnation vary according to the nature of the mate rial to be treated, the nature and concentration of the. impregnating fluid and the kind of finish desired. For convenience the compounds are usually applied from an aqueous medium, but if tightly woven fabrics are to be treated it is frequently advantageous proportion of alcohol or acetone to facilitate penetration of the fabric. It is alsopossible, though for-many purposes undesirable on economic" grounds, to use solutions in organic liquids such, for example, as benzene, ethanol, trichloroethylone, white spirit or mixtures of two or more such liquids. This method of working is advantageously used for the simultaneous dry-cleaning and reproofing of shower-proofed garments.

The concentration of the impregnating fluid to .be used depends on the nature of the material to be treated and the kind of finish desired. 'In general it can be said that softfinishes which are only slightly water-repellent are obtained when the impregnating fluid contains about 0.05 to I l erably contain also an alkaline substance or a substance which has an acid bin'ding action. Al-

ternatively such substances may be applied to the materialseparately, either before or after the impregnation with the quaternary salt. Suitable substances are, for example, pyridine, hexamethylene tetramine and salts of weak acids with ammonia, alkali metals or alkaline earth metals. such as ammonium acetate, sodium acetate or borax.

There may also be added to the treatment bath other textile. finishing agents. for example.

agents which'will give a fuller or stifier handle to the treated materials such as aluminium acetate, carragheen moss, gum tragacanth, resins (natural or synthetic), waxes (in solution or suspension), aluminium stearate, or cellulose derivatives, for example, methyl, ethyl or glycol cellulose. Other water-repellent agents may likewise be added, particularly water-insoluble compounds closely related chemically to the new quaternary salts, for example, diacyl-dianiinoto add to the bath a small quaternary salt.

The treatment is carried out by padding or soaking the material in the impregnating fluid,

removing surplus liquor by squeezing by hydroextract'ing, when necessary drying at a low temperature and then heating for a short time to a temperature sufficient to cause decomposition of the quaternary salt. To obtain the best results the material is finally given a light soap wash, preferably with the addition of a small proportion of ammonia or other alkali, to remove any undecomposed quaternary salt or buffer compounds, together' with any water-soluble decomposition or reaction products.

The finalheat treatment, conveniently to be called the baking treatment, is essential if the softness and water-repellence of the treated material are to be permanent, that is to resist laun dering and dry-cleaning operationsf Good softening and water-repellence may be obtained if the baking step is omitted, but they will not be.

permanent. The baking temperature should be between 90 and 200 0., preferably between 100 and 175 C. The time of baking depends on the temperature used and both depend, to some extent, on the nature of the material being treated. With thick or tightly woven fabrics a longer time of baking at a relatively low baking temperature should be used in order that the heating may be uniform, whereas fabrics of an avoid tendering of the material.

When a hydroxylic solvent or carrying fluid is used, for example water or alcohol, it is desirable, when treating thick or tightly woven fabrics, to dry the impregnated material at a low temperature, for example, 30 to- 50 C., before subjecting it to the baking treatment. The temperature of drying is, however, of less im portance than speed of drying and it is desirable that a brisk circulation of air'around and, so far as is possible, through the fabric, is provided. The aim should be to give as little opportunity as possible for any interaction to take place between hot water or water vapor and the quaternary salt. Such interaction is detrimental -to the final water-repellent. finish. It may be noted, however, that, in respect of their stability to such possible 'decompositiomby water duning the process of application, the new quaternary salts a e superior to those the use of which is described in British Specifications Nos. 466.817, 477,991, 493,920. 495,025, 497,856 and 498.287. With the new compounds (except when applied to thick or tightly woven fabrics), if there is provided a brisk circulation of air around and through the material, th drying step may be omitted, the impregnated material being heated forthwith at the baking temperature.

By a further feature of the invention the new quaternary salts may also be applied to textiles which are of vegetable origin or which are composed of regenerated cellulose in conjunction with compounds which are used in known mannerto make such textiles crease-resistant. Textiles made crease-resistant by the known processes feel harsh to the touch and are stiffer than is desirable. It has been proposed to overcome this difliculty by the incorporation of softening agents but the known softening agents are unsuitable for this purpose because many of them are decomposed by the heat-treatment which is the final stage of the crease-proofing process and others, even if stable to the heat-treatment, are readily removed from the treated materials by laundering or dry-cleaning operations. By the process of the present invention there are provided textiles which are crease-resistant, waterrepellent, soft and supple, readily falling into pleasing folds. Moreover, these properties are resistant to laundering and dry-cleaning operations.

The water-proofing and the crease-proofing processes both involve an impregnation of the material, usually from an aqueous bath, a drying at low temperature and a. subsequent heating at a higher temperature and the two processes may be carried out simultaneously or separately and in either order.

Suitable crease-proofing processes are those in which there is formation of a synthetic resin in situ by impregnation of the fabric with a partly condensed resinous condensation product derived from an aldehyde or aldehyde-yielding substance and urea, thiourea or a urea or thiourea derivative or aphenol, or an amio derivative of 1:3:5- triazine or a substitution product thereof (for example, melamine) under neutral, acid or alkaline conditions, or with the components required be omitted.

This feature of the invention therefore comprises the treatment of textiles whichare of vegetable origin or which are composed of regenera ted cellulose with solutions or suspensions of the new quaternary salts before or after or simultaneously with a treatment with a medium comprising resin-forming components or a partlycondensed resinous condensation product and,

where necessary, an acid or acid-yielding sub-' stance, this process or processes being followed by drying, preferably at low temperature. and finally by a heat treatment at a temperature sufficient to cause decomposition of the quaternary salt and to insolubilize the resin.

- The invention is illustrated but'not limited by the following examples in which the parts areby weight.

Example 1 Medium quality plain calico is padded in a solution of 20 parts of N:N-di-(N'-chloro-triethylammoniomethyl) -distearyl diaminomethane of formula w 1 CuHu-C o-N-cnrmc mn-ml H I CnHss-C 0-N.-CH:N(C1J'!|)|C] (conveniently madeas described in Example 2 of my copending application, Serial No. 286,944)

and 6 parts of crystalline sodium acetate in 1000 The impregnated material is Example 2 A viscose rayon fabric is soaked in a solution of 1 part of N:N-di-(N'-chloro-triethylammoniomethyl)-distearyldiaminomethane and 0.3 part of crystalline sodium acetate in 1000 parts ofreadily falls into pleasing folds.

If it is desired to make the finish resistant to washing and dry-cleaning, the dried fabric is heated for 2 /2 minutes at 150 C. Alternatively the drying step is omitted, the impregnated fabric being heated forthwith for 10 to 15 minutes in a brisk current of air at 150 C.

Example 3 minutes at C. in a solution of 1 part of soap and 0.25 part of strong ammonia solution (sp. gr. 0.880) in 1000 parts of water, well rinsed and dried.

The fabric is now soft and highly water-repellent, these properties being resistant to laundering and dry-cleaning operations.

Example 4 The procedure 'is the same as in Example 1,

' but treating a wool delaine material instead of the calico. v v

Thewoollen material is thereby made soft and highly water-repellent, these properties surviving laundering and dry-cleaning operations.

Example 5 A solution is made by dissolving 100 parts of urea in 200 parts of neutralized 40% aqueous formaldehyde solution to which is added 7.5 parts of concentrated ammonia solution (sp. gr. 0.880). The mixture is boiled for a few minutes and then rapidly cooled to room temperature. A cold aqueous solution of 6 parts of ammonium dihydrogen phosphate and 0.5 part of N:N-di-(N'-chloropyridinomethyl) distearyl diaminomethane of I the formula C "Ear-C ONCH;N I

A J (L1 in 50 parts or water is now added and the whole is diluted to a total volume of 400 parts withcold water.

Spun viscose fabric is impregnated with this solution, squeezed and dried in a current of air at 40 C. and is then heated for 3 minutes at 140 C. superfluous resin is removed by heating the fabric for 5 minutes at 50 C. in a solution containing 2 parts of soap and 1 part of sodium carbonate per 1000 parts of water. The fabric is then rinsed and dried.

The fabric is now soft and highly resistant to creasing. These properties survive laundering and dry-cleaning operations Example 6 parts of urea are dissolved in 200 parts of a neutralized 40% aqueous, formaldehyde solution and 7.5 parts of ammonia (sp. gr. 0.880) are add-.

1 ed. The mixture is boiled for a few minutes and then rapidly cooled to room temperature. 6 parts of ammonium dihydrogen phosphate dissolved in 50 parts of cold water are added and the whole is diluted with cold water to a total volume of 400 parts.

Spun viscose is impregnated with this solution, squeezed until it is double its initial weight, dried in a current of air at 40 C. and then heated'for 3 minutes at C. The so-treated fabric is then padded in a solution of 2 parts of NzN-di- (N-chloro-pyridinomethyl) distearyl diaminomethane and 0.6 part of crystalline sodium acetate per 100 parts of water, squeezed until it is double its dry weight, dried in a current of air at 40 to 50 C. and heated for 3. minutes at 140 C. Finally the material is washed for 5 minutes at 40 C. in a solution of 1 part of soap and 0.25 part of ammonia solution (sp. gr. 0.880) per 1000 parts of water, well rinsed and dried.

The fabric is soft, crease-resistant and waterrepellent. These properties are not destroyed by laundering or dry-cleaning operations.

Eqrample' 7 -C. The fabric is then impregnated with a solution containing urea, formaldehyde, ammonia and ammonium-dihydrogen phosphate prepared as described in Example 6, squeezed until it is double its dry weight, dried at 50 to 60C. and then heated for 3 minutes at 140 C. Finally the fabric is washed for-5 minutes at 50 C. in a solution of 2 parts of soap and 1 part of sodium carbonate per 100 parts of water, well rinsed in warm .water and dried.

The fabric is now soft, water-repellent and crease resistant. These properties are not destroyed by laundering or dry-cleaning treatments I claim:

1. Process for improving the surface characteristics of textile material, which comprises impregnating said material with an organic ammonium compound of the formula:

wherein R stands for an aliphatic hydrocarbon halogen and N(tert) stands for a tertiary amine of the group consisting of aliphatic and heterocyclic tertiary amines, and subsequently submitting the impregnated material to a dry heat treatment at a temperature between 90 and 200 2. A process of treating textile materials for the purpose of modifying the physical characteristics thereof, which comprises impregnating the material with a quaternary ammonium compound of. thegeneral formula wherein R stands for an aliphatic hydrocarbon radical containing at least 7 carbon atoms, X is halogen and N(tert) stands for a tertiary amine selected from the group consisting of aliphatic and heterocyclic tertiary amines, and subse quently submitting the impregnated material to a dry heat treatment at a temperature between 100 and 140 c. Y

3. A process fontreating textile fiber'i'or the purpose of imparting thereto the quality of water-repellence, which comprises impregnating 1 the fabric with an aqueous solution, of not less than 0.5% concentration, of a quaternary ammoniumcomp'ound of the general formula R-C o-m-cni-mmnyx I H? n-c N-C Hr-N mm-x wherein It stands for an aliphatic hydrocarbon radical containing at least "1 carbon atoms, X'i's halogen and 'N(tert) stands for a tertiaryamine selected from the group consisting ofaliphatic and heterocyclic tertiary amines), and thensubmitting the impregnated fiber to a .dry' heat treat- -ment at a temperature between 100 and1'75 C.

4. A process of treating textile materials for. the purpose of modifying thelphysical characteristics thereof, which comprises impregnating the 100 and 140 C.

5. A process for treating textile fiber for the purpose of imparting thereto the quality of water-repellence, which comprises impregnating the fabric with an aqueous solution, of not less than 0.5% concentration, of N,N-di(N'-chloro-pyridinomethyl) -distearyl-diamino-methane, and then submitting the impregnated fiber to a dry heat treatment at a temperature between 100 and 175 C.

6. A process for. treating textile fiber for the purpose of imparting thereto the quality of water-repellence, which comprises impregnating the fabric with an aqueous solution, of not less than 0- concentration, of N,N- di(N' -chloro-tri ethylammoifiomethyl) distearyl-diamino-methane, and' the n submitting the impregnated fiber to 'a dry heat treatment'at a temperature between l00 and*17- C.

7. 'lextilematerial resulting from'the treatment defined in claim 2, and being characterized by soft feel and water-repellent qualities. '8. Textile material resulting from the treatment defined in. claim 4, and being characterized by soft'feel and water-repellent qualities.

9. Textile material resulting from the treatment defined in claim 5, and being characterized by softfeel and water-repellent qualities.

5 10. Textile material resulting from the treatment defined in claim 6, and being characterized l by soft feel andwater-repellent qualities.

THOROLD 

